Selective hydrogenation of aromatic hydrocarbons to cycloolefins

ABSTRACT

A PROCESS IS PROVIDED FOR THE PREPARATION OF A CYCLOOLEFIN WHICH COMPRISES THE PARTIAL HYDROGENATION OF AN AROMATIC HYDROCARBON IN AN AQUEOUS ALKALINE SOLUTION IN THE PRESENCE OF A REDUCED CATALYST FORMED FROM A COMPOUND OF A GROUP VIII METAL. THE HYDROGENATION CAN BE CARRIED OUT BY ADDING TO THE CATALYST SYSTEM A CATION SUCH AS THAT PROVIDED BY ZINC CHLORIDE OR CHROMOUS CHLORIDE OR A CARBONYL OF CHROMIUM, MOLYBDENUM OR TUNGSTEN OR BOTH THE CATION AND THE CARBONYL.

United States Patent 3,767,720 SELECTIVE HYDROGENATION 0F AROMATIC HYDROCARBONS T0 CYCLOOLEFINS William Charles Drinkard, Jr., Orange, Tex., assignor to g. du Pont de Nemours and Company, Wilmington,

No Drawing. Continuation-impart of abandoned application Ser. No. 138,801, Apr. 29, 1971. This application Feb. 25, 1972, Ser. No. 229,565

Int. Cl. C07c /10 US. Cl. 260-667 14 Claims ABSTRACT OF THE DISCLOSURE A process is provided for the preparation of a cycloolefin which comprises the partial hydrogenation of an aromatic hydrocarbon in an aqueous alkaline solution in the presence of a reduced catalyst formed from a compound of a Group VIII metal. The hydrogenation can be carried out by adding to the catalyst system a cation such as that provided by zinc chloride or chromous chloride or a carbonyl of chromium, molybdenum or tungsten or both the cation and the carbonyl.

CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of US. patent applcation Ser. No. 138,801, now abandoned, filed Apr. 29, 1971 by William Charles Drinkard, Jr.

BACKGROUND OF THE INVENTION The invention relates to the preparation of cycloolefins and more particularly to the preparation of cyclohexene.

Hitherto a cycloolefin such as cyclohexene has been obtained by dehydration of cyclohexanol or by dehydrohalogenation of chlorocyclohexane. It is well known that preparation of a cycloolefin by partial reduction of a non-condensed aromatic ring is diflicult to accomplish, in that the resulting olefin or diolefin is usually more easily reduced than the original aromatic compound. However, a process has been described in US. Pat. 3,391,206 for preparation of cyclohexene by partially hydrogenating benzene in the presence of a lower alcohol as a solvent and a ruthenium catalyst. Also, preparation of a tetrahydrophthalic acid by partial hydrogenation of the monoalkali salt of the corresponding phthalic acid in the presence of a ruthenium catalyst has been described in US. Pat. 3,162,679.

Improved methods for preparing cycloolefins continue to be sought. Methods which would be based on low cost starting materials such as benzene, toluene or the xylenes and wherein the cycloolefin would be prepared in an aqueous system providing easy isolation of the reduction products are especially desirable.

STATEMENT OF INVENTION It has been discovered that cycloolefins can be prepared by partial hydrogenation of the corresponding aromatic compound in the presence of water, an alkaline agent and a catalyst comprising a reduced cation of a Group VHI element.

The hydrogenations can be carried out at atmospheric pressure or at pressures below or above atmospheric, in the range, for example, of about 0.01 to about 500 atmospheres. The reaction can be carried out batch-Wise or continuously, in the liquid phase or in vapor phase, and at temperatures in the range of about 0 C. to about 250 C.

The catalyst compositions comprise reduced cations of the Group VIII elements of the Periodic Chart, namely,

"ice

iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum or mixtures thereof.

The reducing agents are those which are more electropositive than the Group VIII element and include such metals as zinc, aluminum, magnesium, lithium, sodium, potassium, rubidium, calcium, strontium, barium and thorium and such compounds as titanium trichloride, sodium borohydride, chromous chloride or ferrous chloride. Depending on the particular Group VIII element to be reduced, hydrogen may also be used.

The term alkaline agent is intended to mean one which in water gives an aqueous solution having a pH value greater than 7.5. Alkalinity may be supplied by alkaline agents which include the hydroxides and oxides of the alkali metals lithium, sodium, potassium, rubidium and cesium, of the alkaline earth metals calcium, strontium and barium as well as ammonia and water soluble organic bases such as methylamine, dimethylamine, diethylamine, tripropylamine, alkylene diamines such as ethylene or propylene diamine, pyridine and the quaternary ammonium bases. The alkaline agent may be used individually or if desired a mixture of two or more individual alkaline agents may be employed in a given hydrogenation. As will be discussed below, the hydrogenation can be carried out with the catalyst on a support. In the case wherein the support is itself basic, alkalinity for the hydrogenation may be provided at least partially by the basic support. In general, alkalinity will be provided by the added alkaline agent.

The hydrogenation can be carride out by introducing into the reactor in addition to the catalyst system and the aqueous alkaline solution a cation of the group consisting of Zn++ cri -i Hg-F Hgl-i' Ni'F-I' Mo++ Fe++ Fe+++, Co++ and Cu+ in an amount from about 0.01 to about 1.0 mole percent, based on the molar amount of the catalyst compound added to the reactor; Suitable compounds of this type include the chlorides, bromides and sulfates of the above-mentioned cations.

The hydrogenation can also be carried out in the added presence of a carbonyl of chromium, molybdenum or tungsten, in an amount from about 0.01 to about 1.0 mole percent based on the molar amount of the aromatic compound being hydrogenated. Alternately the hydrogenation can be carried out using both a cation as mentioned above and a carbonyl or a mixture of cations or carbonyl or mixed cations and mixed carbonyls.

The aromatic compound to be partially hydrogenated can be a monocyclic aromatic hydrocarbon or substituted monocyclic aromatic hydrocarbon of the general formula C H ,,A wherein A is at least one radical of the group of hydrogen, halogen,

CF3, CH3COH6, R, on, i3-R and -0(R):-CH5, where R is a phenyl or alkyl group having one to six carbon atoms, n is an integer of 1-3 and R is an alkyl group of one to four carbon atoms.

Typical monocyclic aromatic hydrocarbons include benzene, toluene, ortho-, metaand para-xylene. Typical substituted monocyclic aromatic hydrocarbons include alkoxyand phenoxy-substituted hydrocarbons such as anisole, phenetole and diphenyl ether, such compounds as acetophenone benzophenone, diphenylmethane, fluorobenzene, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene as well as benzene substituted with at least two different halogen atoms, with CF;, or with aralkyl groups such as C'(CH C H 3 'z) z s s 4 9 z s s- The hydrogenations are carried out in any suitable apparatus and can be done batch wise or continuously. By

one process a salt of the catalyst metal is charged into the reactor, the reactor is flushed with an inert gas such as nitrogen, a portion of the water is added to dissolve the salt after which or along with which the reducing agent is introduced either as a solid or as an aqueous solution. Following the reduction of the catalyst metal compound the alkaline agent is added either as solid or solution and hydrogen flow is then started. The catalyst compound can also be reduced in a separate operation and introduced into the reactor through a dropping funnel or other appropriate device. The aromatice compound to be hydrogenated can be introduced into the reactor along with the other reactants or separately prior to start of the hydrogen flow. At the desired interruption point the reaction product can be separated from the catalyst system by decantation and further refined by distallation.

As indicated above, the catalyst can be used in the hydrogenation as a fixed bed or fluidized system such as a slurry or gaseous dispersion. Typical supports for fixed bed systems include molecular sieves, MgO, Mg(OH) MgCO Ca(OH) CaCO BaCO MnCO NiCO- CoCO ZNO, TiO A1 and tale. The support can be basic, acidic or neutral. Especially favorable results are obtained with the catalyst on a support which is basic wherein, as methode above, the alkalinity is supplied at least partially by the support.

The partially hydrogenated products such as cyclohexene are useful as intermediates in commercially important processes such as conversion into cyclohexanol or adipic acid.

DESCRIPTION OF PREFERRED EMBODIMENTS In the preferred embodiments of this invention the reduced catalyst compositions are derived from ruthenium, rhodium and palladium compounds such as RuCl RhCl or PdC12, or their hydrates. Especially preferred are the reduced catalyst compositions derived from ruthenium.

It is preferred that the water/alkaline agent system be in the fom of an aqueous solution having a pH of at least 11.0; the preferred alkaline agents are the hydroxides 0f the alkali metals such as LiOH, NaOH and KOH.

The preferred reducing agents are TiCl CrCl NaBI-I zinc and hydrogen. The hydrogenations are preferably carried out at a temperature in the range of 25 C. to 200 C. and at a hydrogen pressure of one to about 100 atmospheres. Preferred aromatic compounds for the partial hydrogenation are benzene, toluene and the xylenes.

The preferred range of optionally added cation used with the catalyst system is from about 0.03 to about 0.15 mole percent based on molar amount of the catalyst metal. Preferred compounds for this purpose are the chlorides of the cations as mentioned. The preferred amount of carbonyl for use with the catalyst system if from about 0.03 to about 0.15 mole percent based on molar amount of compound being hydrogenated. Best conversions and yields of the desired cycloolefins are realized with use of both the cation and the carbonyl with the catalyst system.

SECTION A Hydrogenation with aqueous alkaline solution and Group VIII metal catalyst In Examples 1 to 27 the hydrogenations are run in a reaction vessel fitted with stirrer, a side arm for supplying hydrogen below the liquid surface, a gas exit fitted with a bubbler tube to prevent entry of air, a side arm fitted with a serum cap for introduction of liquids by syringe and a large bore dropping tunnel for introduction of solids. The stirrer blades and baffie are coated with Tefion polytetrafiuoroethylene resin. In each example the salt of the catalyst metal is charged to the vessel, the vessel is sealed and sparged with nitrogen after which a portion of the water is added to dissolve the salt following which the reducing agent is added. Base is then added either as solid by quickly opening the system with nitrogen lyst and 1S analyzed by gas chromatography on an F. & M. Model 700 Gas chromatograph. The stainless steel gas chromatograph column (8' x A" OD.) is packed with 20% Carbowax 6000 on Chromosorb P, 60/80 mesh (Applied Science Laboratories, Inc.) and maintained at 70 C. with a 150 mL/minute helium flow rate. The injection port and thermal conductivity detector were maintained at 270 C. and 210 C. respectively. Cyclohexene eluted with a retention time of about 3 /2 minutes. Examples 28 to 39 are carried out in a 100 ml. threeneck flask fitted with a side arm for a serum cap, gas inlet tube above liquid level and a gas outlet through a bubler to exclude air. The third neck is stoppered and used when solids are added. The reaction mixture in stirred with a magnetic stirring bar coated with Tefion polytetrafiuoroethylene resin. For Examples 1-39 hydrogen is supplied at atmospheric pressure, temperature is held at C. and time of reaction is 5 hours except that Example 28 is 9 hours, Examples 29 and 33 is 22 hours, 25 34 is 6.25 hours, Example 34 is 4 hours, Example 36 is 16 hours, and Examples 37-39 is 17 hours. A charge of 20 ml. of benzene is used in Examples 28-39; for the other examples the charge of benzene is 10 ml. The added catalyst compound is 0.26 g. of RuCl -3H O for all of these examples.

TABLE 1 [Hydrogenation of benzene (atmospheric pressure)] Product (percent) Ex. Reducing agent Alkaline agent Water (ml.) Conv. Cyene T1011, 0.3 g. L1OH,3.7 g. 40 66.7 4 2- 101- 0.3 g. CsOH, 10 mm 30 40. 5 10 3- T1011, 0.3 g. Ba(OH)2, 3.0 g. 40 43. 3 4 4"--- T1011, 0.3 g. 01:02, 5.0 g. 40 19.8 s 5- T1013, 0.3 g. NaOH, 0.3 g. 10 22. 5 15 6- T1011, 0.3 g. NaOH, 6.2 g. 40 32. 2 10 T1013, 0.3 g. NaOH, 9.3 g. 60 32.4 s T1011, 0.3 g. NaOH, 6.2 g. 40 9.6 31 5 9 T1011. 0.3 g. NaOH, 0.3 g. 00 9.7 31

T1011, 0.3 g. NaOH, 12.4 g. 8o 8. 25 31 11- F5011, 0.2 g. NaOH, 4.0 g. 40 0. 0 7 12- NaBH1, 0.2 g. NaOH, 6.2 g. 40 33. 1 1 13. b, 0.1 g. NaOH, 0.2 g. 4.0 44. 2 2 14 h, 0.2 g NaOH, 5.2 g. 40 20. 7 1 15 FeCh, 1.2 g NaOH, 4.0 g. 40 6. 5 35 1.6. T1013, 0.3 g NaOH, 8.5 1111. 31. 5 4.3 51 17---. NaBH4, 0.1g. NaOH, 8.5 m1. 31.5 19.3 1 18-.-. Zn, 0.1 g. NaOH, 8.5 mm 31. 5 2. 5 44 10--.- Al, 0.1 g. NaOH, 8.5 1111. 31. 5 35. 5 3 20- Th, 02 g. NaOH, 3.5 mm 31. 5 32. 6 1 21- T1013, 0.3 g NaOH, 8.5 1111. 31. 5 8. 5 35 22-.-- T1013, 0.3 g NaOH, 10 1111. 30 5.9 40 23- Nb, 0.1 g. NaOH, 8.5 ml. 31. 5 30. 7 1 24- Fe, 0.025 g. NaOH, 8.5 mm 31.5 3.3 11 25- T10 0.3 g. NaOH, 1 1111. 39 so 3 20- T1011, 0.3 g. NaOH, 4 1111. 36 37 11 27---. T1013, 0.3 g. NaOH, 10 1111. 30 7.5 as s T 0.3 g. aOH, 0.6 g. 10 4.3 16. 7 0.3 g. NaOH, 1.0 g. 10 11.3 5. 1 0.3 g. NaOH, 0.3 g. 10 79.5 5 0.3 g. NaOH, 1.0 g. 10 33. 5 10 0.3 g. NaOH, 1.4 g. 10 22. 5 20 H4, 0.2 g NaOH, 0.5 g. 10 2. 45 2 NBBH4, 0.2 g KOH, 0.7 g. 10 3.12 4. 5 T1013, 0.3 g. NaOH, 0.8 g. 10 0. 0 11. e 1013, 0.3 g. NaOH, 0.5 g. 10 8. 0 22. 5 NaBHr, 0.1 g. NH4OH, 2.5 ml. 7. 5 0. s1 15. 5 NHBH4, 0.1 g. NH4OH, 5 ml. 5. 0 0. 33 40. 5 39---- N8BH4, 0.1 g. NHioH, 7.5 ml. 2.5 0.17 35. 3

1 Conv.=Converslon; Gyene= Cyclohexene.

2 53% solution. B 50% aqueous solution.

sparge or by adding a solution of base in water through the serum cap. The compound to be reduced is added with the catalyst ingredients or after the base is added prior to starting the hydrogen flow .The crude organic layer is separated from the Water layer containing residual cata- Examples 40 to summarized in Table 2 are carried out in a 10 ml. stainless steel pressure tube coated with Teflon polytetrafiuoroethylene resin. The catalyst compound reducing agent, water and benzene are charged into the tube under nitrogen purge; after reduction is accomsieve by Cyene sieves above with substitution of the molecular the particular support of the example. The catalyst metal represents approximately 6% of the weight of the composite.

TABLE 2 [Hydrogenation of benzene (in pressure tubes)] Product (percent) Water Benzene Reducing agent Alkaline agent (ml.) (ml.) Conv.

plished, the alkaline agent is introduced. The tube is Added catalyst compound closed, cooled in Dry Ice, evacuated briefly and charged with nitrogen at 100 atmospheres and held at 100 C. for 8 hours in Examples -43 and -48 and at 100 C. for

Example 0 2 em "L333 00110 J c m m uuumu I I l 1 1 I I I I aeee aeee mmmmmm mmmmmmmm e wzr r lmmmmmm 21wm1210 338 338 8 338 wna y u u 0000 n 1. & .H mme au aanmma h hn NaOH in Exas described above.

the particular support is illustrated amples 96-107, summarized in Table 4. For the hyd a Hastelloy C reduced with NaBH4 mesh size 12-18; Cu, 0.88.

d at a temperature of 175 C. The catalyst sysem in each case is ruthenium on To prepare the ruthenium on molecular sieve catalyst mentioned in the example, all of which are prepared as The effect of concentration of sodium hydroxide conv1s1onUnion Carbide Corporation) followed by slow 7 centration on yield of cyclohexene .s.i. an is used as the reaction vesse The hydrogenations described in Examples 81 to 95 and summarized in Table 3 are carried out as described with hydrogen at 100 atmospheres and held at 25 60 for Examples 40 to 80 except that a 240 ml. Hastelloy C. for 15 hours in Example and at 100 C. for 15 Cyclohexane. sieve, Linde Division, Union Carbide Corporation, 3 Eu on 13X molecular sieve, Linde molecular sieve, reduced with NaBHr. 4 50% Aqueous solution.

M. Woelm. Esehwege, Germany, Alupharm Chemicals. refrigeration grade, Grade 408,

s, Hastelloy tube (240 ml.). pressure, 200 atmospheres, 175, 5 hrs. Hastelloy tube (240 ml). BIBS.

C shaker tube is always used as the reaction vessel. All hydrogenations are carried out under hydrogen at 750 psi an t described for Example 41 and for Examples 52, 53 and 54. In each case approximately 6% by weight of the catalyst system represents ruthenium.

drogenations described in these examples a charge of 100 ml. of benzene is used, temperature is held at 175 C. and hydrogen is supplied at 750 p with hydrogen at 5 0 atmospheres imilar other examples of the specification there is added to a stirred solution of 20.0 g. of RuCl -3H O in 500 ml. of water 100 g. of 4A powdered molecular sieves (Linde Molecular .SieveLinde Died out as described for molecular shaker tube Conversion; Cyene a, Grace Davidson Chemical, PA400 7 Ru on 02100 gen at. atmospheres, reaction then held at 25 C. for 15 hours. similar to but run at C. for 5 hour ydrogen pressure, 400 atmos Hydrogen pressure, 200 atmospheres.

is carri Conv.

Ru on 4A molecular 5 Ru on basic alumina, cationotropic aluminum oxide, activity Grade 1 Ru on silic Ru on SK, 40 molecular sieve, Union Carbide International Co.

' Ru on 3A molecular sieve.

Run on 3A molecular sieve.

ll Ru on 10X molecular sieve.

* Ru on 4A molecular sieve.

15 Reduced with hydro H 31% NaOH 1: 2%% aqueous solution, hydrogen 15 hours in Example 44 and held at 175 C. for 5 hours in Examples 49-69 and 72-73 hours in Examples 71 and 74. The tube is cooled, vented and the product recovered and analyzed by gas chromatography.

for Example 41 and s addition of 5.0 g. of NaBH The mixture is stirred under nitrogen for one hour, filtered and the residue washed three times with water and thereafter vacuum dried. The preparation of ruthenium on other supports for Examples 52, 53 and 54 TABLE 3 [Hydrogenation of benzene over ruthenium on various supports] Catalyst Product Water Benzene Time Example Support Weight (g.) Alkaline agent (1111.) (ml) (hrs.) Conv. Cyene s1 Mg(OH)z 0.2 NaOH,2Om1. 20 100 17 27.8 40.3 1201 0.2 NaOH, 20110. 20 100 17 as 43.5 CaOO; 0.2 NaOH, 20110. 20 100 17 18.2 39.4 MgCO; 0.2 NaOH,20ml. 20 100 17 6.0 51.1 BaCO 0.2 1030112011111 20 100 17' 7.7 51.1 M7100. 05 1700113011111 20 2 01.7 7.0 N100. 0.5 NaOH,20n1l. 20 10 2 7.2 16.0 COCO; 0.5 NaOH,20ml. 20 10 2 2.3 39.0 0.2 NaOH, 20 1111. 20 100 17 15.0 36.2 ZnO 0.2 NaOH, 20 1111. 20 100 17 4.2 43.4 T1071 0.5 NaOH 011.11. 20 10 2 8.0 57.4 A120; 0.5 NaOH,15rnl. 25 100 5 71.4 9.7 None 3 0.5 NaOH, 20 ml. 20 100 5 11.7 7.2 Talc 0.2 NaOH, ml. 25 100 17 17.2 38.5 95 Mg() 02 NaOH, 151111. 25 100 7 1.5 60.3

1 3107,J aqueous solution. 3 4.4. molecular sieve. 3 Approx.

TABLE 4 {Hydrogenation of benzene-Efiect of NaOH concentration] 31% NaOH Product (percent) Water solution Time Example Catalyst (ml (1111.) (hrs.) Conv. Cyene 96 Ru on Mg(OH)2, 0.2 g. 20 20 17 27.8 49.3 Ru on MgtOEDz, 0.2 g. 15 17 54. 0 38. 9 Bu on Mg(OH)z, 0.2 g. 10 17 93. 7 15. 3 Ru on Mg(OH)z, 0.1 g. 30 10 17 27. 7 52. 9 Ru on Mg(OH)z, 0.1 g. 5 17 23. 8 17. 3 Ru on Mg(OH)z, 0.1g. 0 5 45. 2 13.3 Ru on Mg [LH)2, 0.1 g. 0 0 5 55. 7 1. 9 Ru on A1201, 0.1 g. 40 0 5 30. 0 33. o Ru on A1202, 0.1 g. 0 0 5 100 0 Ru on ZnO, 0.1 g. 40 0 5 3. 4 52.7 Ru on ZlOz, 0.1 g. 40 0 5 8. 9 24. 5 107 Ru on talc, 0.1 g. 40 0 5 17. 1 15. 6

Example 108 35 6% is Under a nitrogen purge a reaction flask is charged CH1 with 0.26 g. of RuCl -3H O, 0.3 g. of TiCl 6.2 g. of NaOH, 40 ml. of H 0, and 10 ml. of toluene. The mixture is maintained at 25 C. with hydrogen bubbled 0 through the reaction at 1 atmosphere for 5 hours. Gas 4 chromatographic analysis shows that the crude organic layer contains 2.2% hydrogenation products of which d 13% i 77% is CH: 4.5 CH;

Example 110 CH;

In a nitrogen purge 0.026 g. of RuCl -3H O, 0.03 g. of TiCl 0.8 ml. of NaOH 50% solution, 3.1 ml. of H O, and 2 ml. of toluene are charged to a pressure tube as described in Example 109. The tube is closed, cooled in Dry Ice, evacuated briefly, charged with hydrogen to 50 atmospheres, and held at 175 C. for 5 hours and the and 12% 1s products recovered. Gas chromatographm analysis shows CH3 that the crude organic layer contains 25% hydrogenation products of which 53% is Example 109 In a nitrogen purge 0.5 g. of ruthenium on 4A molecand 39% is ular sieve, prepared as in Example 41, 0.2 g. of NaOH, CH 1 ml. of H 0, and 5 ml. of toluene are charged to a 10 s 1111., stainless steel pressure tube coated with Tefion. The tube is closed, cooled in Dry Ice, evacuated briefly, charged with hydrogen to 100 atmospheres and held at 100 C. for 8 hours. The tube is cooled, vented, and the and 3% 15 products recovered. Gas chromatographic analysis shows CH3 that the crude organic layer contains 10.0% hydrogenation products of which is C. I Q .5

Example 1 11 and 40% is CH3 CH8 1 Example 112 In a nitrogen purge charge 0.026 g. of RuCl -3H O, 0.03 g. of TiC1 0.8 ml. of NaOH 50% solution, 3.1 ml. of H 0, and 2 ml. of p-xylene are charged to a 10 ml., stainless steel pressure tube and hydrogenation is carried out as described in Example 110. Gas chromatographic analysis shows that the crude organic layer contains 19% hydrogenation products of which 85% is CH: and its isomer and 15% is Hag...

Example 113 In a nitrogen purge 0.1 g. of Ru on CaCO (prepared as described in Example 54), 0.37 g. of LiOH, 4 ml. of H 0, and 2 ml. of toluene are charged to a 10 ml., stainless steel pressure tube and hydrogenation is carried out as described in Example 110. Gas chromatographic analysis shows that the crude organic layer contains 39% hydrogenation products of which 97% is methyl cyclohexane and 3% is Example 114 In a nitrogen purge 1.0 g. of RuC1 -3H O, 2 ml. of pyridine, 10 ml. of H 0, and 40 ml. of benzene are charged to a 400 ml., stainless steel pressure tube. The tube is closed, cooled in Dry Ice, evacuated briefly,

10 charged with hydrogen to atmospheres, held at 100 C. for 15 hours, cooled, vented,and the products'recovered. Gas chromatographic analysis shows that the crude organic layer contains 6.9% hydrogenation products of which 5.3% is cyclohexene and 94.7% is cyclohexane.

Example Continuous hydrogenation of benzene.This run is carried out in a glass column equipped with a shaft fitted alternately with stirrer blades and metal discs to act as baffles, as well as vertical baffles along the Wall to provide better mixing. The stirrers and bafiles are coated with Teflon polytetrafluoroethylene resin. In the operation the reactor system is purged well with nitrogen and the column is filled with premixed catalyst. Hydrogen and benzene are fed to the bottom of the column and product recovered by overflow from a lower side arm at the top of the column.

In a typical run the reaction column is charged with a premixed catalyst composed of 0.52 g. of RuCl -3H O, 0.6 g. of TiCl 17 ml. of NaOH (50% by weight in water) and 53 ml. of water. A total of 13 m1. of benzene is fed with a syringe pump at a rate of 6.5 ml. per hour while hydrogen is fed into the column at a rate of about one bubble per second. Pressure of hydrogen at the top of the column is one atmosphere. Temperature is held at 25 C. After two hours gas chromatographic analysis shows the crude product flowing from the column to contain 1.45% of hydrogenation products, of which 46% is cyclohexene and 54% is cyclohexane.

In Examples 116-125 the reactor is charged under a nitrogen purge.

Example 116 Hydrogenation of benzophenone.-The following experiment is carried out in a 10 ml. stainless steel pressure tube coated with Teflon tetrafluoroethylene resin. The tube is charged with 0.026 g. of RuCl -3-H O, 0.03 g. of

TiCl 0.1 g. of benzophenone, 1.0 ml. of cyclohexane, 3.1

ml. of H 0, and 0.8 ml. of 50% aqeuous NaOH in that order. The tube is sealed, cooled in Dry Ice, evacuated briefly, charged with hydrogen at 50 atmospheres at 70 C. and held at 70 C. for 8 hours. The tube is cooled, vented and the product is extracted twice with 5 ml. of cyclohexane. The cyclohexane is evaporated under vacuum and the residue analyzed by gas chromatography. Conversion is complete to give the products shown below Gig-Q QEQ Example 117 1 1 Example 1 l 8 Hydrogenation of trifluoromethylbenzene.-The reaction flask is charged with 0.26 g. of RuCl -3H O, 0.3 g. of TiCl 35 ml. of water, 5 ml. of 50% aqueous NaOH and ml. of trifluoromethylbenzene. The mixture is maintained at C. with hydrogen bubbled through the reaction at 1 atmosphere for 5 hours. Gas chromatographic analysis shows that the crude organic layer contains 2.4% hydrogenation products of which 22.5% is Example 1 19 and its isomers.

Example 120 Hydrogenation of bromobenzene.-The following reaction is run in a glass reactor flask containing Teflon polytetrafluoroethylene resin coated bafiies and stirrer blades. Stirring is at the rate of 1000 r.p.m.

The reaction flask is charged with 0.26 g. of

RuCl 3 H 31.5 ml. of water, 0.3 g. of TiCl 8.5 ml. of 50% aqueous NaOH and 10 ml. of bromobenzene. The mixture is maintained at 25 C. and hydrogen bubbled through the reaction at 1 atmopshere for 4.5 hours. Gas chromatographic analysis shows that the crude organic layer contains 13.3 benzene, 2.9% cyclohexene and 1.7% cyclohexane.

Example 121 Hydrogenation of 1-chlor0-2-fiuorobenzene.-The reaction flask is charged with 0.26 g. of RuCl -3H O, 31.5 ml. of H 0, 0.3 g. of TiC1 8.5 ml. of 50% aqueous NaOH, 10 ml. of toluene and 2.0 g. of l-chloro-Z-fiuorobenzene. The mixture is maintained at 25 C. with hydrogen bubbled through the reaction at 1 atmosphere for 5 hours. Gas chromatographic analysis shows that the crude organic layer contains 2.8% cyclohexane, 3.7% cyelohexene, 5.3% benzene, and 6.2% fluorobenzene giving a total conversion of 18%. Thus of the aromatic hydrogenated 33% is cyclohexane and 67% is cyclohexene.

Example 122 Hydrogen of p-dichlorobenzene.-The reaction is carried out by the same procedure as that for Example 121,

12 but with 5.0 g. of p-dichlorobenzene. Gas chromatographic analysis shows that the crude organic layer contains 0.3% cyclohexane, 0.9% cyclohexene, 3.6% benzene and 5.1% chlorobenzene giving a total conversion of 9.9%. Thus, of the aromatic hydrogenated 25% is cyclohexane and is cyclohexene.

Example 123 Hydrogenation of m-dichlorobenzene.'1'he reaction is carried out by the same procedure as that for Example 121, but with 3.88 ml. of m-dichlorobenzene. Gas chromatographic analysis shows that the crude organic layer contains 1.2% cyclohexane, 1.4% cyclohexene, 11.0% benzene, and 7.9% chlorobenzene giving a total conversion of 21.5%. Thus, of the aromatic hydrogenated 46% is cyclohexane and 54% is cyclohexene.

Example 124 Hydrogenation of o-dichlorobenzene.The reaction is carried out by the same procedure as that for Example 121 but with 3.83 ml. of o-dichlorobenzene. Gas chromatographic analysis shows that the crude organic layer contains 2.7% cyclohexane, 2.2% cyclohexene, 21.1% benzene, and 11.7% chlorobenzene giving a total conversion of 38%. Thus, of the aromatic hydrogenated 55% is cyclohexane and 45% is cyclohexene.

Example 125 1-chloro-3-fiuorobenzene.-The reaction is carried out by the same procedure as that for Example 121, but with 2.0 g. of 1-chloro-3-fluorobenzene. Gas chromatographic analysis shows that the crude organic layer contains 0.5% cyclohexane, 0.7% cyclohexene, 7.1% benzene and 13% fluorobenzene, giving a total conversion of 21%. Thus, of the aromatic hydrogenated 41% is cyclohexane and 59% is cyclohexene.

SECTION B Hydrogenation with aqueous alkaline solution, Group VIII metal catalyst and cationic modifier (1) ZnCl as modifier (Table 5) The hydrogenations described in Examples 1 to 4 are carried out in a glass reactor under hydrogen at atmospheric pressure, as described under Section A for Examples 1-27.

Examples 5-6 are carried out in a laboratory reactor which comprises a Jurguson sight glass fitted with a circulating pump in a closed loop, a means for air-free introduction of reactants, ports for sampling and means for continuous monitoring of temperature and pressure, with total capacity of about 1000 m1.

Examples 7-13, showing particularly the efiect of increasing amounts of the promoter, are carried out in a stainless steel pressure tube.

TABLE 5 [Hydrogenations with zinc chloride modifier] Benzene Cyene 1 Added catalyst Reducing Zn Ch Benzene H20 NaOH Temp. Hydrogen Time converted yield Ex. compound agent (g.) (1111.) (mL) (1111.) C.) (p.s.i.) (hrs) (percent) (percent) RuCl33H2O, 0.26 g- T1013, 0.3 g 0. 3 10 40 25 4. 5 1. 53 S4 RuClzSHzO, 0.26 g. Ti C13, 0.3 g- 0. 2 10 31.5 8. 5 25 5 2. 0 7 2 RHCIflSHQO, 0.26 g. Ti C13, 0.3 g. 0. 1 10 81.5 8. 5 25 5 1. 26 74 Ruck-SE20, 0.19 g. TiCla, 0.3 g 0. 05 20 20 1. 8 25 5 O. 23 78 RuCl -3H2O, 3.22 g- T1013, 3.72 g 4. 8 124 496 76. 9 ca 49 48 5 5. 4 83 RuC13-3H2O, 3.22 g- T1013, 3.72 g- 9. 6 124 495 76. 9 ea 94 48 5 20 65 RuCh'3HzO, 1.07 g- T1613, 1.24 g- 1.13 124 83 12. 8 175 3, 000 3 57 33 RuCls-3HzO, 1.07 g T101 1.24 g. 0 124 83 12. 8 175 3, 000 3 99 3. 2 R11, 5.0 g. 0 41. 3 165 25. 6 125 750 3 0 R11, 5.0 g. 0. 80 41. 3 165 25. 6 750 3 9. 5 76 Ru, 5.0 g 1. 6 41. 3 25. 6 125 750 3 25 62 Ru; 5.0 g-.. 2. 4 41. 3 165 25. s 125 750 a 24 62 13 R11, 5.0 g 3. 2 41. 3 165 25. 6 125 750 3 12 80 1 Cyene=0yclohexene. I 1 atmosphere. 8 6.2 grams.

4 50% aqueous solution.

6 Eu on 4A molecular sieve.

(2) Other cationic modifiers.The hydrogenations described in Examples 14 to 26 and summarized in Table 6 are carried out in a 240 ml. Hastelloy C shaker tube. A charge of 0.035 g. of catalyst compound RuCl '3H O, 0.04 g. of TiCl as reducing agent, 100 ml. of benzene, 25 g. of water and 15 ml. of 31% aqueous solution of NaOH is used in each case with the several cationic promoters. The hydrogenations are run in a stainless steel pressure tube under a hydrogenation pressure of 750 p.s.i. at 175 C. for various periods of time shown in the table.

TABLE 6 [Eflect of various cationic modifiers on hydrogenation] Benzene Cyclo- Ttme, converted hexene Example Promoter, g. (hrs.) (percent) (percent) (3) Catalyst supported on molecular sieves.The hydrogenations of Examples 27-33 are carried out in a laboratory reactor, as described for Examples 5-6 above.

Example 27 This example illustrates hydrogenation wherein the catalyst compound is reduced on a molecular sieve with hydrogen. In a reactor purified with nitrogen a mixture of 3.2 g. RuCl -3H O, 76.9 g. NaOH in 400 ml. H 0, and 15 g. of 4A powdered molecular sieve is treated with hydrogen at 48 psi. for 1 hour. At the end of this time a solution of 4.8 g. ZnCl in 96 ml. H and 124 ml. of benzene is added and hydrogenation is carried out under hydrogen at 48 p.s.i. for 5 hours at 55 C. Analysis of the crude organic layer by gas chromatography reveals that it contains 3.1% hydrogenation products of which 12% is cyclohexene and 88 %is cyclohexane.

Examples 28-33 (Table 7) The Ru on molecular sieve catalyst for these examples is prepared as described for Example 41 (Section A).

TABLE 7 14 tube is cooled, vented and the product recovered. Gas chromatographic analysis shows that the crude organic product contains 3% cyclohexene and 97 cyclohexane. Total converison is 29.75%.

Example 35 Example 36 Following the procedure of Example 35 a charge of 0.1 g. of ruthenium on CaCO 0.05 g. of ZnCl 0.8 ml. of aqueous NaOH, 3 ml. of water and 2 ml. of benzene is found on gas chromatographic analysis of the crude organic layer to give 39.25% of hydrogenation products of which 64% is cyclohexene and 36% is cyclohexane.

Example 37 Following the procedure of Example 35 a charge of 0.1 g. of ruthenium on 10X molecular sieve, 0.1 g. of ZnCl 0.8 ml. of 50% aqueous NaOH, 3 ml. of water and 2 ml. of p-xylene is found to give 2% of cyclic olefin products of which 14% is Example 38 Following the procedure of Example 35, a charge of 0.3 g. of ruthenium on CaCO 0.05 g. of ZnCl 0.8 ml. of 50% aqueous NaOH, 3 m1. of water, and 2 ml. of toluene is found to give 15% hydrogenation products of which 61% is methyl cyclohexane, 27% is [Efiect of ZnGl; modifier, catalyst on molecular sieve-various temperatures and pressures] Product (percent) ZnClz N aOH Water Benzene Tempera- Pressure (g.) (g.) (ml) (1111.) ture C.) (p.s.i.) Hours Conv. Cyene t 8 76. 9 496 129 ea. 50 47 5 3. 4 34 1. 6 76. 9 496 124 ca. 48 5 27. 5 23 1. 6 25. 6 165 41. 3 100 750 3 7. 6 75 1. 6 25. 6 155 41. 3 175 750 3 s5 13 1. e 25. e 155 41. s 125 300 a 46 40 1. 6 25. 6 165 41. a 125 1500 3 12 53 On molecular sieves prepared as described above.

(4) Other combinations.The hydrogenations of and 12% is Examples 34-38 are carried out in a 10 ml. stainless steel CH3 pressure tube coated with Teflon polytetrafluoroethylene l resin and the tube is charged under nitrogen purge. 6

Example 34 SECTION C This example illustrates the use of palladium as catalyst with zinc chloride as promoter and wherein the catalyst compound is reduced with hydrogen.

A charge of 0.2 g. of PdCl 0.1 g. of ZnCl 0T g. of NaOH, 2.5 ml. of H 0, and 2.5 ml. of benzene is placed in a pressure tube. The tube is closed, cooled in Dry Ice, evacuated briefly and charged with hydrogen at 100 The hydrogenations of Examples 1-36, summarized in Table 8, are carried out at 25 C. in a glass reactor with hydrogen supplied at atmospheric pressure, as described atmospheres and maintained at 100 C. for 8 hours. The under Section A for Examples 1-27.

Product(percent) Water Benzene Time (1111.) (mL) Gus.) Conv. Gyene TABLE 8 [Hydrogenation of benzene-use of carbonyl with catalyst system] Carbonyl Reducing agent Alkaline agent complex Added catalyst compound 247 .463 .9 44775650L 4 67 0107 5 L .5 .1 .5 L .7. 5 2 6 5 2 4 3 1 l l 26 823% B 7021 B%%Lfl%www% 0 0 BB 55555555555555555550885505555255 5 5555 5 5 5 l 5 2 5 3 5 55 L 1 L A ll 7 L 5 1115705 .URWZHZHHTMMZ H .Hm .7H11 2 2 2 5 a 2 awww 626 2 22 mw. mm mmw ase 1 1 1 1 222 1 5 0 00000058854400000500 .55555555000 00000000 000 0 0O 0 0 0000 21121112 .11111 .113 zlml4444222m222mmn wmnmmmwwzzwpdmnzmw zzzn 221 12 1 1 1.1.11 5.10 500536611500000500 5055555005 5000000 0 0 0 .34 41 2 86641 3 4 .w w w 111111.Jml mmmmmwmmmmmmmmlmmmmml 3 3 3222 11 1 61 1 11 ggeeea ac eeeae .gg.gg..... Egg %%%222 g 4ggggggggggggggggggggfifi2g2. gg66666gggg8gggw=gggggg 22 2223 M5Q 43333 4 342442244233222 50 .2 .22 .2AA 22 00 3 00 .03200000000333333333333331653 .a o aaaaauuaaouoaaoacaoaonaa 2 5.3.1... .oooooooooooooooooofl w mmmwmmmwmmmb \whhhhhhhhhhhhkhhhh\mkhhhmwmww mmmmmwmwmmmm m w .mh mhh m m mm h n CCC OOOOOOOOOOOOOOOOOOOOOOOOO O C OOOOOOOOOOOOOOOOOOO aaam ammwwww www wwwww m mwwww m mmuwwmw wmmwwwwwww wwwwwwwmwwmmm MMMCCCCWWWW C CMMMM M MMMWWWWWWW WWWWOOC 1 w 1 (or uwwuuuwwuuuwwwwwwuwwwwmM w n a wWWWwWw A 2 2 z a a.. n r .1 aeaeeee e .ae e 5? 1.111 .o mm mm m g w m m mmmm mg w g w g g m 53255235323 02 332302A35nmosm5e232555 5e 3 0 88 8 e 88 88 6 0 e l llllllfl 4-60l 200ll1010068 88H H 00LL000L0 0 00 O 0 0 0 0 0 0 L00 0 00 0 LO 0 HHHHHHHHHHHHHanaHHEaaaaaammumaaamn moonaamaaaam a H H H ma Hanna HERRHEKHE n wwwwwwwe.wwwe.wwwwwwwwwwwwfiwwwwwwwwwwamwfiwwwwwwmm wfi wwwwwwwwwwwwwww a v l v a 4 a NNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNMNNNNNNNNNNNNNNNNNNN m u x m m n u 25: 8 m g w m w h w g lma wvag vwew ev ac ggn v wUvZ S Wm e. g e evvw w w w fi mana es d 3 .33 .33 .22 .21233333 332A 32 32233333n "33333 333 .6 13522 m 00000 0000000000000m0000000000000 00w 00 00H Hum000 mw0m000000nmw0000 hs a ha lws hafosqa hms hafm mhhhhhaf hx a mhh ,0 00 l l In r ,5 .l y L mz hb l l l a c 111 l 111 11 ll l 111 L111 1 a... h 3 1 1 0 0 3 M11 b 3 s mmwmwmcmwmmcommwcmmw cmmcccmc cwmhcmmmm cc mmq wm cmm w mmwcwwmwm mowm m m l. .l 11.11.11. .1. 11 111.11.1 1 1 .1l.l.1.1 1 1 1 1 1 1 1 11 1 1 TTTTTTT TTTTTTTTTTTNTTTTTTT T TTT TTH HTTTTTFNNNTTTVNTATNSTFFFFNTTTT m w .m e C d V. a q m avew wnwuwawuwevnwowvwvwwwvvawawnwaw awawmamaewqvwwew cwnwuw .owawwwawanaew vwwwwwuwvwvwewuwnwnwawwwuvuwewww awcwuv n W ouwmaaanaazzaaamaawaaaamaaaaz aaa wrm 0 0 0 0 0 0 0 0 0 000 00 0 fi0 0 000000000000 LLLL0000000000000000000000000 0 00 CM mmnwwwwnnmwwfiwwwe. wwwwfiwwwwwwnmm on o no o n n nnonwno HHH H H. 1 HH as z...z 2...... 21 a 2 2.. I 2 ilc 3. .33twaafimtmafiammaammm m mfimmmmmmmmmmamfiaaammmammmmm mm we a a e vs m w mm c R R Wm m 0 C B 123 Example The hydrogenations for Examples 37-40 are run at with hydrogen at atmospheres, then held at 175 C. 100 C. in a 400 ml. stainless steel pressure tube coated for 5 hours. Gas chromatographic analysis shows the rewith Teflon polytetrafiuoroethylene resin, under hydrocovered crude organic layer to contain 9% of cyclic olegen pressure of 100 atmospheres. The hydrogenation for finproducts of which 36% is Examples 41-69 are carried out in the glass apparatus described for Examples 1-36, with hydrogen supplied at 0H8 atmospheric pressure. The temperature for Examples l- 36 and 41-69 is 25 C.

The hydrogenations in Examples 70-75 are carried out Example 71 in a 10 ml. stainless steel pressure tube coated wi Following the procedure of Example a charge of Teflon polytetrafluoroethylene resin. The tube is charged 0.1 g. of ruthenium on 10X molecular sieve, 0.05 g. of under nitrogen purge. W(CO) 1.0 g. of KOH, 3 ml. of water and 2 ml. of

Example, 70 benzene shows 12.7% hydrogenated products of which 57% is cyclohexene and 43% is cyclohexane.

A charge of 0.1 g. of ruthenium on 10X molecular E 1 72 sieve, prepared as described in Example 19, 0.05 g. of Xampe W(CO)6. 0.8 ml. of 50% aqueous NaOH, 3 ml. of H 0, Following the procedure of Example 7, a charge of and 2 ml. of p-xylene is placed in a pressure tube. The M 0.1 g. of ruthenium on 10X molecular sieve, 0.05 g. of tube is closed, cooled in Dry Ice evacuated briefly, charged W(CO) 0.8 ml. of 50% aqueous NaQH, 3 ml. of H 0,

18 and 2 m1. of toluene shows 7% hydrogenation products 4% is indicated to be of which 42% is methyl cyclohexane, 49% is CH3 and 15% is indicated to be and 9% is CH;

10 CH3 6 O SECTION D Example 73 Hydrogenation with aqueous alkaline solution, Group VIII Following the procedure of Example 70 a charge of metal catalyst, a cationic modifier and a carbonyl of 0.3 g. of ruthenium on silica, 0.05 g. of W(CO) 0.8 m1. chromlum molybdenum or tungsten of 50% aqueous NaOH, 3 ml. of H 0, and 2 ml. of ben- The hydrogenations of Examples 1-30, summarized in zone shows 4.6% hydrogenation products of which 90% Table 9, are carried out in the glass reactor described in is cyclohexane and 10% is cyclohexene. Section A for Examples 1-27. The hydrogenations are run TABLE 9 [Hydrogenation of benzene with cationic promoter and carbonyl complex] Product (percent) Cationic Water Benzene Time Example Reducing agent Alkaline agent Carbonyl complex promoter (ml.) (1111.) (hrs.) Conv. Cyene 'IiCla, 0.3 g. NaOH, 6.2 g. W(CO)u 0.3 g. ZnClz, 0.3 g. 40 10 5 0. 39 88 TiCla, 0.3 g. NaOH, 6.2 g. W(CO)0, 0.3 g. ZnClz, 0.1 g. 40 10 5 0. 85 82 TiCla, 0.3 g. NnOH, 6.2 g. W(CO)c, 0.3 g. ZnClg, 0.2 g. 40 10 5 0.7 86 TiCh, 0.5 g. NaOH, 6.2 g. W(CO)s, 0.3 g. ZI1C12, 0.1 g. 40 10 5 0. 42 75 'IiCl 0.2 g. NaOI-I, 6.2 g. W(CO)u, 0.3 g. ZnOlz, 0.1 g. 40 10 5 0. 39 83 TiCls, 0.4 g. NaOH, 6.2 g. W(OO)s, 0.3 g. ZnClz, 0.1 g. 40 10 5 0.41 85 TiCla, 0.3 g. NaOH, 9.0 g. W(CO)0, 0.3 g. ZnClr, 0.1 g. 40 10 5 0. 4 87 TiOh, 0.3 g. NaOH,8.0 g. W(CO)u, 0.3 g. .nOlz, 0.1 g. 40 10 5 0.5 85 TiClz, 0.3 g. NaOH, 7.0 g. W(C0)u, 0.3 g. ZllClz, 0.1 g. 40 10 5 1. 3 80 TiCl 0.3 g. NaOH, 5.0 g. W(CO)0, 0.3 g. ZIlClz, 0.1 g. 40 10 5 1. 85 83 TlCl3, 0.3 g. NuOH, 4.0 g. W(C0)o, 0.3 g. ZnClz 0.1 g. 40 10 5 3. 75 78 T1013, 0.3 g. NaOH, 3.0 g. W(CO)0, 0.3 g. nClz, 0.1 g. 40 10 5 1. 2 80 TiCls, 0.3 g. NaOH, 2.0 g. W(CO)e, 0.3 g. ZnOlz, 0.1 g. 40 10 5 1. 74 T1013, 0.3 g. NaOH, 1.0 g. w o0)i, 0.3 g. ZnClz, 0.1 g. 10 5 1. 5 15 TiCls, 0.3 g. NaOH, 6.2 g. W(CO)0, 0.3 g. ZnGlz, 0.1 g. 40 10 5 2. 33 83 TiOla, 0.3 g. NaOH, 8.5 1111. W(CO) s, 0.3 g. ZnSO4, 0.1 g. 31. 5 10 5 0. 75 84 'IiCla, 0.3 g. NaOH, 8.5 :ml. Mo(OO)s, .26 g. ZnC12, 0.2 g. 31. 5 20 22. 5 1. 75 83 TiCls, 0.3 g. NaOH, 8.5 1131. W(CO)e, 0.3 g ZnC12, 0.2 g. 31. 5 20 22. 5 1. 85 TiC1 0.3 g. NaOH, 8.5 ml. Mo(CO)a, 0.26 g. ZnClz, 0.2 g. 31. 5 10 5 0. 68 82 T1013, 0.3 g. NaOH, 8.5 1111. W(CO)c, 0.3 g ZIlClz, 0.2 g. 31. 5 10 5 0. 83 86 'IiCla, 0.3 g. NaOH, 6.2 g. W(CO)0, 0.3 g ZnC12, 0.2 g. 40 10 5 1. 75 85 TiClQ, 0.45 g. NaOH, 7.0 g. W(CO)s, 0.45 g. ZnCle, 0.2 g. 40 10 5 1. 75 84 TiCl 0.15 g. NaOH, 6.2 g. W oo)., 0.15 g. ZnClz, 0.05 g. 40 10 5 0.0 83 TiC13, 0.3 g NaOH, 4.0 g. W(CO) 0.3 g. ZnClz, 0.1 g. 40 10 5 2. 47 79 T101 0.3 g NaOH, 12.4 g. W(CO)c, 0.3 g. ZnClz, 0.1 g. 70 10 5 0. 78 78 TiC1 0.3 g NaOH, 6.2 g. W(CO)c, 0.3 g. ZnClz, 0.05 g; 40 10 5 1. 1 82 TiOh, 0.3 g NaOH, 6.2 g. or(o0)., 0.2 g. 211012, 0.1 g. 40 10 5 1. 4 s2 TiClz, 0.3 g NaOH, 6.2 g. Mo(C 0.26 g ZnClz, 0.1 g. 40 10 5 0.79 84 TiCl 0.3 g NaOH, 0.2 g. W(CO)s, 0.8 g ZnClz, 0.1 g. 40 10 5 0. 88 87 NaOH, 0.2 g. W(C )6, 0.3 g ZnClz, 0.1 g. 40 10 4. a 2.02 85 1 aqueous solution.

Example 74 at 25 C. with hydrogen being supplied at atmospheric pressure. The amount of catalyst compound, RuCl -3H O g g ifig %f gs igg E zi gg g gi s g gg g charged for Examples 1-21 and 24-30 is 0.26 g.; for lg/(C0); L0 g of KOH 3 m1. of H20 andz of Example 22 the amount is 0.4 g. and for Example 23 the I amount is 0.13 g. In Examples 1-15 there is added to the zene shows 12.7% hydrogenation products of which 57% charge 1 ml. of concentrated hydrochloric acid.

15 cyclohaxene and 43% 1S cyclohexane' For Examples 31-38, the reaction mixture is prepared Example by adding the appropriate amounts of W(CO) and ZnCl Under a nitrogen purge a charge of OJ of with ml. of benzene to a stirred solution of 3.22 g.

Rucl 0, 0.1 of W(CO) OJ of NaOH, 25 m1- of RuCl :3H t) in 250 m1. of water in a reaction flask of 2 25 i of toluege is glued in a pressure flushed with n trogen. To th s is added T1Cl through an tube as described in Example 70. The tube is charged with alr'free P fulmel Winch Washed in with 24 hydrogen at 100 atmospheres and held at for 8 of benzene. Stirring 1s cont1nued .for 10 minutes followed houm Gas chromatographic analysis of the recovered by addition of a solution of 76.9 g. of NaOI-I in 246 ml.

product shows it to contain 15.9% hydrogenation prodof Water T i i into 3 equal portions nets of which 81% is 70 each of which is used in individual runs to follow.

O Example 31 In a nitrogen purge a catalyst mixture, prepared as described above, containing 1.07 g. RuCl '3H O, 1.24 g.

1 Grace Davidson Chemical Silica Gel PA 400; Refrigeration 7 W(CO)6 T1Cl3 Zncl? NaOH Grad. Mesh Size 12 2S; C 0 gg% ml. of water and 41.3 ml. of benzene are charged to a Examples 3 2-3 8 In these examples the amounts of RuCl -3H O, TiCl water and benzene are as shown in Example 31. The amounts of other reactants, reaction conditions and product analyses are summarized in Table 10.

TABLE What is claimed is:

1. A process for converting a monocyclic aromatic compound to a cyclic monoolefin, the aromatic compound having the formula C H ,,A,, wherein A is at least one radical from the group consisting of hydrogen, halogen,

wherein R' is an alkyl group of one to four carbon atoms, R is of the group consisting of phenyl and alkyl groups having one to six carbon atoms and n is an integer of 13, which comprises partially hydrogenating the aro- {Hydrogenation with added cationic promoter and carbonyl complex-elevated temperature and pressure] Hydrogen Tempera- Product (percent) W(CO) ZnCl; N aOH pressure ture Time (g) (g.) (g.) (p.s.1.) 0.) (hrs) Conv. Cyene 0. 35 2. 27 25. 5 750 125 a 50 55 1. 24 1.5 25. 6 1,500 225 a 59 24 1.. 24 1. 5 25.5 a, 000 175 a 11. a 15 1. 24 a 2 25. o 750 175 a 4. 5 as 1. 24 1. e 25. 5 750 175 1 9 s1 0. 3a 2. 25 12. so 750 175 s a7 65 0. 35 2. 25 51. a 750 175 3 41 57 Example 39 matte compound m a reactor under a hydrogen pressure A catalyst on 4A molecular sieves is prepared as described in Example 41 (Section A).

Fifteen grams of the catalyst mixture, 3.72 g. W(CO) 4.78 g. ZnCl 76.9 g. NaOH in 496 m1. of water and 124 ml. benzene is charged under nitrogen to a laboratory reactor (Section B-Examples 5-6). After being thoroughly flushed with hydrogen the reaction mixture is heated to 55 C. and pressured with hydrogen to 48 p.s.i. These conditions are maintained for 22 hours after which time the organic layer is recovered and analyzed by gas chromatography. Analysis of the crude product shows 26.5% hydrogenation products of which 32% is cyclohexene and 68% is cyclohexane.

Example 40 A catalyst mixture, prepared as described in Example 39, containing 5.0 g. Ru-on-molecular sieves, 0.67 g. W(CO) 1.6 g. ZnCl 25.6 g. NaOH in 165 ml. of water and 41.3 ml. benzene are charged under nitrogen to a 330 ml. stainless steel pressure tube. After being cooled and evacuated, the tube is heated to 100 C. and pressured with hydrogen to 750 p.s.i. These conditions are maintained for 3 hours after which time the reaction mixture is recovered and analyzed by gas chromatogra hy. Analysis of the crude organic product shows 2% hydrogenation products of which 81% is cyclohexene and 19% is cyclohexane.

Example 41 In a nitrogen purge 0.1 g. of ruthenium on CaCO 0.05 g. of ZnCl 0.05 g. of W(CO) 0.8 m]. of 50% aqueous NaOI-I, 3 ml. of water and 2 ml. of benzene are charged to a 10 ml., stainless steel pressure tube coated with Teflon. The tube is closed, cooled in Dry Ice, evacuated briefly, charged with hydrogen at 50 atmospheres and held at 175 C. for 5 hours. Gas chromatographic analysis shows that the crude organic layer recovered to contain 2.48% hydrogenation products of which 51% is cyclohexene and 49% is cyclohexane.

Example 42 Following the procedure of Example 41 a charge of 0.1 g. of ruthenium on 10X molecular sieve, 0.05 g. of ZnCl 0.05 g. of W(CO) 0.37 g. of LiOH, 3 ml. of water and 2 ml. of benzene shows 5.47% hydrogenation products of which 31% is cyclohexene and 69% is cyclohexane.

in the range of about 0.1 to about 500 atmospheres and at a temperature in the range of about 0 C. to about 250 C., in the presence of water and an alkaline agent and a catalyst comprising at least one reduced cation of a Group VIII element.

2. The process of claim 1 wherein the water and the alkaline agent constitute an aqueous solution having a pH with numerical value greater than 7.5.

3. The process of claim 2 wherein the aqueous alkaline solution is a solution of an alkali metal hydroxide.

4. The process of claim 3 wherein the Group VIII element is of the group consisting of ruthenium, rhodium and palladium.

S. The process of claim 4 wherein the Group VIH element is ruthenium.

6. The process of claim 3 wherein the compound of the Group VIII metal is reduced with an agent of the group consisting of T101 NaBH CrCl FeCl Li, Na, K, Rb, Ca, Sr, Ba, Th, Al, Mg, Zn and hydrogen.

7. The process of claim 6 wherein the reducing agent is of the group consisting of TiCl CrCi NaBH zinc and hydrogen.

8. The process of claim 7 wherein the aromatic compound is of the group consisting of benzene, toluene and the xylenes.

9. The process of claim 5 wherein there is introduced into the reactor, in addition to the reduced cation of a Group VIII element, a cation of the group consisting f i++ w Co++ and Cu+ in an amount from about 0.1 to about 1.0 mole percent, based on the molar amount of the reduced cation of Group VIH element.

10. The process of claim 5 wherein the hydrogenation is carried out in the added presence of a carbonyl of a metal of the group consisting of chromium, molybdenum and tungsten, in an amount from about 0.01 to about 1.0 mole percent based on the molar amount of the aromatic compound being hydrogenated.

11. The process of claim 9 wherein the hydrogenation is carried out in the added presence of a carbonyl of a metal of the group consisting of chromium, molybdenum and tungsten, in an amount from about 0.01 to about 1.0 mole percent based on the molar amount of the aromatic compound being hydrogenated.

12. The process of claim 9 wherein the aromatic compound is of the group consisting of benzene, toluene and the xylenes.

21 13. The process of claim 10 wherein the aromatic compound is of the group consisting of benzene, toluene and the xylenes.

14. The process of claim 11 wherein the aromatic compound is of the group consisting of benzene, toluene and the xylenes.

References Cited UNITED STATES PATENTS 3,531,536 9/ 1970 Gerhold 260667 3,183,278 5/1965 Koch, Ir. 260-667 2,846,488 8/1958 Miller 260-667 22 3,391,206 6/ 1968 Hartog 260-666 3,594,307 7/1971 Kirk 208-57 FOREIGN PATENTS 5 252,638 6/1964 Australia 260667 711,742 6/ 1965 Canada 260667 DELBERT E. GANTZ, Primary Examiner J. M. NELSON, Assistant Examiner US. Cl. X.R. 208-143 mg STATES PATENT OFFICE @ERTHFECATE 0F (IQRECTION Patent No. 3,7 7g7 Dated 3; 973

Inventor(s) William Charles Drinkerd, Jr.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 20, line 58, "0.1" should be --0.01--.

Signed and sealed this 19th day of March 1974.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. C. MARSHALL DANN Attesting Officer I Commissioner of Patents 

